Lubricating composition



Patented Nov. 22, 1 938 LUBRIGATING COMPOSITION- Carl F. Prutton,Cleveland, and Albert K. Smith,

Shaker Heights, Ohio, assignors, by mesne assignments, to The Lubporation, Cleveland, Delaware ri-Zol Development Cor- Ohio, acorporation of No Drawing. Application July 16, 1935,

Serial No. 31,720

18 Claims.

In U. S. Patent Nos. 1,986,645 and 1,986,651 it is taught that thelubricating properties of a lubricating composition may be materiallyimproved and extreme pressure characteristics imparted to lubricantssuch as mineral lubricating oil, by the addition thereto of minoramounts of halogenated carbon ring compounds.

It has been explained that the reason why such compounds thus improvethe extreme pressure characteristics of the lubricant probably is due tothe fact that such addition agents chemically react with the bearingsurfaces under the conditions imposed by relative movement and extremepressure between the bearing surfaces to form a microscopic film of ametallic halide which prevents seizing between the bearing surfaces byacting as an anti-fluxing agent.

The halogenated carbon ring compounds were indicated as preferable insaid patents due to the fact that such compounds are relativelystable, 1. e., they do not readily hydrolyze in the presence of moisturewhich usually occurs in varying quantities in mineral oils. In otherwords, the halogenated carbon ring compounds are sufliciently stable sothat decomposition and attack thereof upon the metallic surfaces occursonly in the areas where extreme pressure is encountered, i. e., onthebearing surfaces.

One theory of the action of halogen compounds, specifically chlorinecompounds, in increasing film strength, assumes that, as aboveindicated, under the'stress of the rubbing action of bearing surfaces inmotion under load, chlorides of the bearing metals are formed on theirsurfaces and exert an anti-fluxing effect in preventing subsequentfusing of the two surfaces. This surface reaction, however, to takeplace with suificient efiectiveness depends upon the hydrolysis of thechlorine compound as a simultaneous intermediate reaction. Thesereactions may be expressed as follows:-

ably would act to reduce one or more of the organic compounds ratherthan to appear as free hydrogen.)

The correctness of the foregoing theory is substantiated by the factthat when a chlorinated hydrocarbon is added to a hydrocarbon mineraloil and the mixture thoroughly freed from moisture, by the action ofdehydrating agents, the 5 film strength is no more than that of the oilalone. Exposure of the mixture to the atmosphere so that it may absorb aslight amount of moisture will then cause an increase in the filmstrength.

Since the presence of a large amount of moisture and especially of freewater is objectionable in a lubricant besides being a highly variablefactor in normal service, it is advisable to supply an oil solublesubstitute for the same.

It is the principal object of this invention, therefore, to provide alubricating composition of the type utilizing halogenated organiccompounds as the extreme pressure addition'agent but so modified as tobe effective in the manner defined without being dependent upon thepresence in the lubricating composition of some addition material suchas water.

Other objects of our invention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, said invention,then consists of the means hereinafter fully described and particularlypointed out in the claims. 7

The following description sets forth in detail one approved combinationof ingredients embodying our invention, such disclosed meansconstituting, however, but one of various forms in which the principleof the invention may be used.

Broadly stated, this invention comprises the use as a lubricant ofoxygen and halogen bearing organic compounds and more specifically,oxygen and halogen bearing organic ring compounds, either used alone orincorporated with any suitable oil base.

The oxygen which is included in the molecule of the addition agent actsto increase the effectiveness of the latter in raising the film strengthof a mineral oilto which the addition agent is added or to improve thelubricating properties of the halogenated compound when used without theaddition of some other lubricant. The oxygen probably acts in the sameway as water in making possible the formation of hydrochloric acid as anintermediate step in the surface reaction above explained.

By combining in a single molecule the halogen and the oxygen atoms, alubricant is affected in two ways:

First: The oxygen is always available at the exact point where required;and

Second: The molecule is more strongly adsorbed by metal surfaces thansimilar halogen compounds which do not-contain oxygen.

The latter circumstance enhances the eflect of small amounts of suchcompounds because it is equivalent to an increase in concentration ofthe compound at the bearing surfaces.

We have found that certain oxygen-containing organic ring compoundswhich have been chlorinated and added to a lubricating oil are capableof improving the properties of such oil, particularly when employed forthin-film lubricating purposes. The addition of these certain oxygencontaining organic ring compounds which have been chlorinated and addedto the lubricating oil have been found to improve. the propertiesthereof to an even greater extent than certain similar chlorinatedhydro-carbons, notably when added in very small amounts.

The halogen and oxygen-containing organic ring compounds added to asuitable oil base are, as above indicated, preferably of the chlorinatedspecies and particularly the compounds which have been found toproducevery satisfactory re sults, may be classified as follows; vizz,

I. Carbon ring" type compounds (e? g. decahydronaphthalene,tetrahydronaphthalene etc.). (3) Naphthenes, naphthenic acid, etc. (0)Of mixed type such as oxygen and halogenbearing derivatives of indene,hydrindene, hydranthracene, etc.

[1. "Heterogeneous ring type compounds (G) 0f the aromatic or alliedtype including oxygen and halogen-bearing derivatives of .pyridine,quinoline, etc.

(b) Other types such as oxygen and halogenbearing derivatives of furanand its derivatives and of thiophene, pyrrole etc.

Included in Class H are two principal types of compounds, viz:-Comp0undsin which all of the ring structures are of the heterogeneous type andcompounds containing both heterogeneous ring structures and carbon ring/structures.

The foregoing compounds may also be classifled according to the natureof the attachment of the oxygen to the compound, viz:-

I. Directly attached to one or more carbon atoms, as in the case of r(1') Ethers and analogous compounds (2') Compounds containing the -=-COHradicle, such as alcohols and other derivatives of carbinol (includingphenols, cresols, naphthols etc.)

(3') Compounds containing the carbonyl (=C=O) radicle, such asaldehydes, ketones, organic acids, esters and salts of organic acids,thio-acids and esters of thlo-acids (4') Compounds in which oxygen formsa part of the ring structure, e. g. furan and its derivatives,anthraquinone,

etc.

II. Indirectly attached through the means of some other atom, i. e., inthe form of an inorganic radicle, e. g.: amide, arsenate,v

arsenite, chlorate, chlorite, cyanate, hydroxylamine, hypochlorite,nitrate, nitrite, nitro, nitroso, perchlorate, phosphate, phosphite,sulphate, sulphite, sulphinic acid, sulphone, sulphonic acid,sulphoxide, thiocyanate, isothiocyanate, thio-sulphate, thio-phosphate,and isocyanate.

The halogen and oxygen-bearing organic ring compounds of the ester andsalt type include compounds of the aromatic type which may be classifiedas follows:

1. Esters and salts of an aromatic acid;

2. Esters formed by the combination of a phenol, cresol, naphthol, etc.with an organic acid of either the fatty or aromatic type:

3. An ester formed by the combination of an aromatic alcohol (eithermono-hydric or poly-hydric) with an organic acid of either the fatty oraromatic type.

In addition to the substltuents containing oxygen, other substituentsmay also be present without destroying and in certain cases, improvingthe effect on the lubricating qualities of the oil such as other arylgroups, alkyl groups, and amino and substituted amino groups, imino,azo, hydrazo, hydrazine, nitrile, mercapto, sulphide, polysulphide.

As a matter of convenience, the halogen and oxygen-containingsubstituted diphenyls, as well as the halogen and oxygen-containingsubstituted benzenes where two or more phenyl groups are directlylinked, may be inclusively referred to as halogen and oxygen-containingsubstituted polyphenyls.

As previously indicated, the foregoing so-called addition agents may,for most uses, be added in minor amounts to other lubricants such asmineral oil, fish oil, lard oil, castor oil, rape-seed oil, etc., and insome cases, depending upon the character of use, as well as thecharacter of the selected agents, the latter may be effectively 'used intheir pure state.

The optimum amount of the halogen compound to be employed is usuallydependent upon various considerations such as its cost, the character ofthe selected compound, the character of the addition agent to which thesame is added and more particularly, the character of the use to whichthe same is put. For most uses, since the cost of such halogen compoundsis usually considerably greater than lubricants such as mineral oil,optimum results are obtained by using minimum quantities of thesehalogenated addition agents. For the purpose of lubricating and reducingthe friction between relatively moving parts of an internal combustionengine such as the remainder of the mechanism by means act-' ing in anauxiliary fashion such as by the addition of the lubricating compositionto the engine fuel, the composition for such purposes will preferablycontain a larger amount of such halogen compounds, i. e., from about 2%to about 10%.

When lubricating bearing surfaces such as gears and the like whereextreme temperatures are usually not encountered a compositioncomprising a major proportion-of a suitable oil base and a total of lessthan about 20% of at least one halogen and oxygen-containing organiccompound of the enumerated class will be found very satisfactory.

When combined with a lubricating oil such as mineral oil, the optimumamount of the halogen compound to be employed will depend largely uponthe halogen content of the particular compound, its physicalcharacteristics and especially its effect on the viscosity of the oil towhich it is added. When addition agents of the above enumerated classhaving very low viscosity are "employed, and added to lubricants such asmineral oil, the limit of the amount of such compounds which may beadded and which will produce' improved results depends in a largemeasure upon the reduction in viscosity of the composition caused by theaddition of such compounds. When, however, the more viscous compoundsare employed, or where the particular use does not require thick filmlubrication, the socalled addition agents may, as previously indicated,be employed in their pure state.

Experiments have shown that when compounds which readily hydrolize, suchas chlorinated open chain compounds, are added to the oily base,hydrolysis will take place to such an extent that the metal parts ofany. machine being lubricated will be seriously attacked and corroded bythe acid generated. On the other hand, the addition of chlorinatedorganic ring compounds of the above enumerated class does not cause corrosion.

Certain of the halogen and oxygen-bearing open chain or aliphaticcompounds, in their pure state, or when added to a suitable base doresult, however, in a lubricant particularly suitable for certainpurposes. Examples of the foregoing are halogenated fatty oils such aschlorinated cottonseed oil and chlorinated cocoanut oil. As aboveindicated, such compounds readily hydrolize andwhile thus not preferredas a lubricant for use in the crankcase of internal combustion enginesare, nevertheless, admirably suited for use as lubricants in metalworking such as drawing, extruding, rolling, etc., where the lubricantis in contact with the metallic surface for only relatively a shortlength of time and where the very slight amount of corrosion which -mayresult is not particularly objectionable.

Furthermore, such compounds are admirably suited for use in lubricantsin die drawing or similarly working certain corrosion resistantmaterials such as. stainless steel and the like.

With regard to the stability of the organic ring compounds contemplated,the most resistant to hydrolysis of the halogen are those in which thehalogen is directly attached to an atom which is part of a benzenoidring structure. Examples of such ring structures are aryl groups such asthe phenyl and naphthyl groups. In any case, for most uses, it ispreferred to have the halogen attached to an atom which is part of anorganic ring structure and especially a six-membered organic ringstructure. v

The compositions comprising our invention have certain advantages whenused as a lubricant of which the following may be mentioned:-

First: By the use of this composition, it is possible to extend thepressure range between the bearing surfaces because of the reducedtendency for bearing surfaces so lubricated to become scored or toseizeat higher pressures than are allowable with ordinary lubricants.

Second: The friction between the bearing surfaces is reduced, especiallyin the higher pressure range, below that obtained with ordinarylubricants.

This application is a continuation in part of co-pending applicationsSerial No. 649,734, filed December 31, 1932, and Serial No. 737,070,filed July 26, 1934.

Other modes of applying the principle of our invention may be employedinstead of the one explained, change being made as regards the ma-.terials employed in carrying out the process, provided the ingredientor ingredients stated in any of the'following claims or the equivalentof such stated ingredient or ingredients be employed.

We, therefore, particularly point out and distinctly claim as ourinvention:-

1. A lubricating composition including as a primary lubricatingconstituent a halogenated oxygen-bearing organic compound in alubricating oil vehicle, said compound having a vapor pressure less thanatmospheric at a temperature of 140 C.

2. A lubricating composition including as a primary lubricatingconstituent a halogenated oxygen-bearing organic ring compound in-alubricating oil vehicle.

3. A lubricating composition including as a primary lubricatingconstituent a halogenated oxygen-bearing aromatic compound in alubricating oil vehicle.

4. A lubricating composition containing as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such composition affecting its use as a lubricant improvedby incorporating therein a minor amount, based on the amount of mineraloil, of a halogenated oxygen-bearing organic compound having a vaporpressure less than atmospheric at a temperature of 140 C.

5. A lubricating composition containing as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such composition affecting its use as a lubricant improvedby incorporating therein a minor amount, based on the amount of mineraloil, of a halogen and oxygen-bearing organic ring compound.

6. A lubricatingcomposition containing as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of 2 V such composition afiecting its use as a lubricantimproved by incorporating therein a minor amount, based on the amount ofmineral oil, of a halogen and oxygen-bearing cycle-aliphatic compound.

8. A lubricating composition containing as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such composition affecting its use as a lubricant improvedby incorporating therein a minor amount, based on the amount of mineraloil, of a halogen and oxygen-bearing hydro-aromatic compound.

9. A lubricating composition containing as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such composition afiecting its use as a lubricant improvedby incorporating therein a minor amount, based on the amount of mineraloil, of a halogen and oxygen-bearing alkylated-aromatic compound.

10. A lubricating composition containing as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such composition affecting its useas a lubricant improvedby incorporating therein a minor amount, based on the amount of mineraloil, of a halogen and oxygen-bearing carbon ring compound.

11. A lubricatingcomposition containing as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such composition aifecting its use as a lubricant improvedby incorporating therein a minor amount, based on the amount of mineraloil, of a halogen and oxygen-bearing bridged ring compound. i

12. A lubricating composition containing as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such composition afiecting its use as a lubricant improvedby incorporating therein an effective amount up to 10%, ased on theamount of mineral oil, of a halogenated oxygen-bearing organic compoundhaving a vapor pressure less than atmospheric at a temperature of 140 C.

13. A lubricating composition containingas a principal lubricatingconstituent a'major amount of mineral lubricating oil with theproperties of such composition affecting its use as-a lubricant improvedby incorporating therein from about 0.25% to about 2%, based on theamount of mineral oil, of a halogenated oxygen-bearing organic compoundhaving a vapor pressure less than atmospheric at a temperature of 140 C.

14, A lubricating composition containing as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such composition afiecting its use as a lubricant improvedby incorporating therein from about 0.25% to about 2%, based on theamount of mineral oil, of a halogen and. oxygen-bearing organic ringcompound.

15. A lubricating composition containing as a principal lubricatingconstituenta major amount of mineral lubricating oil with the propertiesof such composition affecting its use as a lubricant improved byincorporating therein from about 0.25% to about 2%, based on the amountof mineral oil, of a halogen and oiwgen-bearing aromatic compound,

16. A lubricating composition containing as a principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such composition affecting its use as a lubricant improvedby incorporating therein a minor amount, based on the amount ofmineraloil, of a halogen and oxygen-bearing organic compound having a' vaporpressure less than atmospheric at a temperature of 140 C. and being ofthe type in which the halogen is directly attached to a ring structure.V

17. A lubricating composition containing asa principal lubricatingconstituent a major amount of mineral lubricating oil with theproperties of such composition affecting its use as a lubricant improvedby incorporating therein a minor amount, based on the amount of mineraloil, of

such composition aflecting its use as an extreme e pressure lubricantimproved by incorporating therein a minor amount, based on the amount ofmineral oil, of a halogenated oxygen-bearing organic compound having avapor pressure less than atmospheric at a temperature of 140 C.

CARL F. PRUTTON. ALBERT K. SMITH.

